Nonlinear hydrodynamic phenomena in Stokes flow regime

We investigate nonlinear phenomena in dispersed two-phase systems under creeping-flow conditions. We consider nonlinear evolution of a single deformed drop and collective dynamics of arrays of hydrodynamically coupled particles. To explore physical mechanisms of system instabilities, chaotic drop evolution, and structural transitions in particle arrays we use simple models, such as small-deformation equations and effective-medium theory. We find numerical and analytical solutions of the simplified governing equations. The small-deformation equations for drop dynamics are analyzed using results of dynamical systems theory. Our investigations shed new light on the dynamics of complex fluids, where the nonlinearity often stems from the evolving boundary conditions in Stokes flow.     

Antisense-mediated isoform switching of steroid receptor coactivator-1 in the central nucleus of the amygdala of the mouse brain

Background

Antisense oligonucleotide (AON)-mediated exon skipping is a powerful tool to manipulate gene expression. In the present study we investigated the potential of exon skipping by local injection in the central nucleus of the amygdala (CeA) of the mouse brain. As proof of principle we targeted the splicing of steroid receptor coactivator-1 (SRC-1), a protein involved in nuclear receptor function. This nuclear receptor coregulator exists in two splice variants (SRC-1a and SRC-1e) which display differential distribution and opposing activities in the brain, and whose mRNAs differ in a single SRC-1e specific exon.

Methods

For proof of principle of feasibility, we used immunofluorescent stainings to study uptake by different cell types, translocation to the nucleus and potential immunostimulatory effects at different time points after a local injection in the CeA of the mouse brain of a control AON targeting human dystrophin with no targets in the murine brain. To evaluate efficacy we designed an AON targeting the SRC-1e-specific exon and with qPCR analysis we measured the expression ratio of the two splice variants.

Results

We found that AONs were taken up by corticotropin releasing hormone expressing neurons and other cells in the CeA, and translocated into the cell nucleus. Immune responses after AON injection were comparable to those after sterile saline injection. A successful shift of the naturally occurring SRC-1a:SRC-1e expression ratio in favor of SRC-1a was observed, without changes in total SRC-1 expression.

Conclusions

We provide a proof of concept for local neuropharmacological use of exon skipping by manipulating the expression ratio of the two splice variants of SRC-1, which may be used to study nuclear receptor function in specific brain circuits. We established that exon skipping after local injection in the brain is a versatile and useful tool for the manipulation of splice variants for numerous genes that are relevant for brain function.     

Testing Lorentz invariance and CPT conservation with NuMI neutrinos in the MINOS near detector

A search for a sidereal modulation in the MINOS near detector neutrino data was performed. If present, this signature could be a consequence of Lorentz and CPT violation as predicted by the effective field theory called the standard-model extension. No evidence for a sidereal signal in the data set was found, implying that there is no significant change in neutrino propagation that depends on the direction of the neutrino beam in a sun-centered inertial frame. Upper limits on the magnitudes of the Lorentz and CPT violating terms in the standard-model extension lie between 10(-4) and 10(-2) of the maximum expected, assuming a suppression of these signatures by a factor of 10(-17).     

The combinatorial encoding of disjoint convex sets in the plane

We introduce a new combinatorial object, the double-permutation sequence, and use it to encode a family of mutually disjoint compact convex sets in the plane in a way that captures many of its combinatorial properties. We use this encoding to give a new proof of the Edelsbrunner-Sharir theorem that a collection of n compact convex sets in the plane cannot be met by straight lines in more than 2n-2 combinatorially distinct ways. The encoding generalizes the authors’ encoding of point configurations by “allowable sequences” of permutations. Since it applies as well to a collection of compact connected sets with a specified pseudoline arrangement of separators and double tangents, the result extends the Edelsbrunner-Sharir theorem to the case of geometric permutations induced by pseudoline transversals compatible with . Supported in part by NSA grant MDA904-03-I-0087 and PSC-CUNY grant 65440-0034. Supported in part by NSF grant CCR-9732101.     

Stereostructure assignment of flexible five-membered rings by GIAO 13C NMR calculations: prediction of the stereochemistry of elatenyne

The stereochemistry of conformationally mobile five-membered rings is often hard to assign from NMR data, and [2,2']bifuranyl systems are even more challenging. GIAO (13)C NMR chemical shifts have been calculated for a series of [2,2']bifuranyl and pyranopyran species, taking into account their conformational flexibility using weighted averages of the data for all low energy conformers. We show that calculation of (13)C NMR chemical shifts using the geometries obtained using molecular mechanics greatly reduces the computational expense without a significant loss of accuracy, even in this demanding system. The results were sufficiently accurate to distinguish not only the pyran and furanyl isomers but also between all the diastereoisomeric forms. As a result of this validation, we predict the stereochemistry for the recently proposed revised structure of the natural product elatenyne, which contains a [2,2']bifuranyl core.     

Atomic-scale assembly of a heterogeneous catalytic site

The distance between surface Pd atoms has been shown to control the catalytic formation of vinyl acetate from ethylene and acetic acid by AuPd catalysts. Here, we use the bulk alloy's thermodynamic properties, as well as the surface lattice spacing of a AuPd(100) alloy single-crystal model catalyst to control and optimize the concentration of the active site (Pd atom pairs at a specific Pd-Pd distance with Au nearest-neighbors). Scanning tunneling microscopy reveals that sample annealing has a direct effect on the surface Pd arrangements: short-range order preferentially forms Pd pairs located in the c(2 x 2) sites, which are known to be optimal for vinyl acetate synthesis. This effect could be harnessed for future industrial catalyst design.     

Enantioselectivity in the boron aldol reactions of methyl ketones

DFT computed transition states quantitatively explain the surprising stereochemical outcome of unsubstituted enolborinates in diastereoselective and enantioselective boron aldol reactions.     

Structural, solid-state NMR and theoretical studies of the inverse-coordination of lithium chloride using group 13 phosphide hosts

The reaction of MeAlCl2 with 'PhPLi2' in THF gives [{MeAl(PPh)3Li(4).3 THF}4(mu4-Cl)]-Li+ (1). The GaIII and InIII analogues, [{MeE(PPh)3Li(4).3 THF}4(mu4-Cl)]-Li+(THF)3 (E=Ga (2), In (3)), are obtained by the in situ reactions of MeECl2 with PhPLi2 in THF. For all of the complexes, the cage anions have an unusual cubic arrangement that is similar to a zeolite, and contain large voids (ca. 17 A). The location of the Li+ counterions in 1-3 and their coordination environment appears to subtly reflect variations in packing and lattice energy. Whereas in 1 highly mobile, loosely coordinated Li+ counterions are present, 2 and 3 contain less mobile THF-solvated counterions within the cavities. X-ray crystallographic and solid-state NMR studies are reported on 1-3, together with model DFT calculations on the selectivity of halide coordination.